This invention relates to substituted fluorinated aromatic-based polymers having at least one trifluoromethyl or hexafluoroisopropylidene group in the polymer backbone and methods for using and preparing fluorinated monomers, oligomers, and polymers for high performance polymer, electronic, aerospace, coatings, high temperature gas separation, and other applications.
Fluorinated polymer derivatives are of considerable interest due to their unique combinations of electrical and electrooptical properties, thermal stability, and structural versatility. The structures of the starting materials, synthetic methods, physical treatments, and chemical modifications can significantly impact the performance of fluorinated polymer derivatives for specific applications.
Fluorinated polymer derivatives have been synthesized using a number of chemical routes. However, previous fluorinated polymer derivatives have been limited, at least in part, because fluorinated polymers typically have low solubilities. Because of the trade-off between solubility and thermal stability, previous methods have produced materials with relatively poor solubility and/or poor thermal stability. Similarly, previous methods have required high temperatures to effect an efficient polymerization reaction.
While prior fluorinated polymers have exhibited some advantageous properties, they have not had combined properties such as increased solubility, high gas permeability, flexibility, low absorption of water, transparency and fire resistance, while retaining thermal stability. In addition, characterization of previous fluorinated high performance polymers has been limited by interference by other functional groups incorporated in the polymer (ketones, ethers, imides, sulfones, etc.).
What is needed are new fluorinated high performance polymers, oligomers, and copolymers, and block copolymers that combine high solubility, transparency, high gas permeability, low absorption of water, and fire resistance while retaining enhanced thermal stability, exceptional flexibility and transparency, and methods for synthesizing such compounds.
This invention provides new fluorinated high performance polymers and methods for preparing high yields of soluble fluorinated polymer derivatives having enhanced thermal stability and other properties, such as low dielectric constant and minimal moisture absorption, making such polymers useful for a wide range of electronic, aerospace, and other applications.
The fluorinated monomers used to prepare the fluorinated polymers of the invention include, but are not limited to Compounds Ia, Ib, Ic, Id, Ie, If, Ig, Ih and Ij as described below. The fluorinated polymers of the invention include, but are not limited to Compounds IIa, IIb, IIc, IId, IIe, IIf, IIg(1), IIg(2), IIh, IIi and IIj as described below and also include various oligomers, copolymers, and block copolymers made from dihalogenated aromatic-based monomers and/or oligomers.
Also provided herein are methods for synthesizing fluorinated oligomers, polymers, copolymers, and block copolymers. Monomers used to prepare the polymers of the invention may be prepared via any suitable method which provides reasonably high yields. The preferred polymers, copolymers, and block copolymers are prepared via nickel-catalyzed coupling polymerization. The resulting fluorinated polymer derivatives have benzene and fluorine linkages incorporated into the polymer backbone and are suprisingly quite soluble in a variety of solvents, while maintaining high thermal stability and other properties that make the resulting polymer and copolymer materials particularly suitable for a wide range of high performance polymer applications.
Additional objects and advantages of the present invention will be set forth in part in the description that follows, and in part will be obvious from the description, or may be learned through the practice of the invention. The objects and advantages of the invention will be attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.